DE853444C - Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compounds - Google Patents
Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compoundsInfo
- Publication number
- DE853444C DE853444C DEF2700D DEF0002700D DE853444C DE 853444 C DE853444 C DE 853444C DE F2700 D DEF2700 D DE F2700D DE F0002700 D DEF0002700 D DE F0002700D DE 853444 C DE853444 C DE 853444C
- Authority
- DE
- Germany
- Prior art keywords
- benzenesulfonic acid
- alkyl
- acid amide
- preparation
- amide compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von p-alkylsubstituierten Benzolsulfonsäureamidverbindungen Benzolsulfonsäureamide mit einer p-ständigen, durch Halogen in u-Stellung substituierten Alkylgruppe sind bisher unbekannt. Versuche, die p-Alkylbenzolsulfonsäure<tmide in der Alkylgruppe zu halogeniiereti, scheiterten an der Reaktionsfähigkeit der Wasserstotiatome der Sulfonsäureamidegruppe gegenüber diesen Mitteln. Die Umsetzung zwischen beiden Komponenten geht mit großer Heftigkeit vor sich und führt nicht zu den gewünschten (-i-Halogenalkylsulfonamiden.Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compounds Benzenesulfonic acid amides with a p-position substituted by halogen in the u-position Alkyl groups are so far unknown. Attempts to use the p-alkylbenzenesulfonic acid <tmide halogenated in the alkyl group failed because of the reactivity of the Hydrogen stotiatoms of the sulfonic acid amide group versus these agents. The implementation between the two components goes on with great violence and does not lead to the desired (-i-haloalkylsulfonamides.
Es «erde nun gefunden, daß man die im Patent 7-17 99-1 beschriebenen p-(u-Halogenalkyl)-benzolsulfonsäurehalogenide sehr glatt mit Ammoniak oder beliebigen primären oder sekundären Aminen zu p-(u-Halogenalkyl)-benzolsulfonsäureamiden umsetzen kann, wobei man zweckmäßig bei Temperaturen unter 6o° arbeitet. Der einwandfreie Verlauf der Reaktion im Sinne einer alleinigen Umsetzung des Halogens in der Sulfonsäurehalogenidgruppc war sehr überraschend im Hinblick auf die ebenfalls sehr große Umsetzungsfähigkeit des Halogens in a-Halogenalkylgruppen. Die Umsetzung kann unverdünnt oder in einem Lösungs- oder Verdünnungsmittel, z. B. Alkohol, Aceton, Benzol oder auch Wasser, ausgeführt werden. Zur Umsetzung können neben Ammoniak aliphatische, cycloaliphatische, aromatische, aliphatisch-aromatische oder heterocyclische, gegebenenfalls substituierte Amine verwendet werden. Die oben gekennzeichneten Sulfonsäureamide entstehen in nahezu voller Ausbeute. Die so erhaltenen p-(a-Halogenalkyl)-benzolsulfonsäureamide stellen wertvolle Ausgangsstoffe der organisch chemischen Industrie dar.It has now been found that those described in patent 7-1799-1 p- (u-Haloalkyl) -benzenesulfonic acid halides very smoothly with ammonia or any convert primary or secondary amines to p- (u-haloalkyl) -benzenesulfonic acid amides can, and it is expedient to work at temperatures below 6o °. The flawless one Course of the reaction in the sense of a sole conversion of the halogen in the sulfonic acid halide group was very surprising in view of the also very great ability to implement of the halogen in α-haloalkyl groups. The implementation can be neat or in one Solvents or diluents, e.g. B. alcohol, acetone, benzene or water, are executed. In addition to ammonia, aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or heterocyclic, optionally substituted Amines can be used. The sulfonic acid amides identified above are formed in almost full yield. The p- (a-haloalkyl) -benzenesulfonic acid amides thus obtained are valuable raw materials for the organic chemical industry.
Beispiel i In die Lösung von 279 4-Brommethyl-benzolsulfonsäurechlorid in 75 ccm Alkohol werden unter Kühlen und Rühren 20 ccm 2oo/'oige wässerige Ammoniaklösung zutropfen gelassen. Die Temperatur wird unter 20° gehalten und nach Zugabe des Ammoniaks noch io bis 15 Minuten weiter gerührt. Es entsteht ein dicker Kristallbrei des 4-Brommethyl-benzolsulfonsäureamids, das nach dem Absaugen mit Wasser gut ausgewaschen und aus Alkohol umkristallisiert in glänzenden farblosen Kristallen vom Schmelzpunkt i97° erhalten wird. Es besitzt nur mehr einen schwachen benzylchloridartigen Geruch und ist in kalter, verdünnter Natronlauge leicht löslich.EXAMPLE i 20 cc of 2oo / o aqueous ammonia solution are added dropwise to the solution of 279 4-bromomethyl-benzenesulphonic acid chloride in 75 cc of alcohol, with cooling and stirring. The temperature is kept below 20 ° and, after the ammonia has been added, stirring is continued for 10 to 15 minutes. A thick crystal slurry of 4-bromomethylbenzenesulfonic acid amide is formed which, after suctioning off with water, is washed out well and recrystallized from alcohol in glossy, colorless crystals with a melting point of 97 °. It only has a weak benzyl chloride-like odor and is easily soluble in cold, dilute sodium hydroxide solution.
Verwendet man anstatt des Ammoniaks Dimethylamin, so erhält man das 4-Brommethyl-benzolsulfonsäuredimethylamid in farblosen Nadeln vom Schmelzpunkt 115°, die in Natronlauge unlöslich sind.If you use dimethylamine instead of ammonia, this is what you get 4-Bromomethylbenzenesulfonsäuredimethylamid in colorless needles with a melting point 115 °, which are insoluble in sodium hydroxide solution.
'Beispiel 2 27 g 4-Brommethyl-benzolsulfonsäurechlorid werden in 75 ccm Aceton gelöst und mit einer Lösung von 21 g Benzylamin in 50 ccm Aceton versetzt. Die Mischung erwärmt sich. Bei zu raschem Zusammenbringen der beiden Reaktionskomponenten kommt das Aceton zum Sieden- Nach halbständigem Kochen auf dem Wasserbad wird die von Kristallen des gebildeten Benzylaminhydrochlorids erfüllte Lösung mit Wasser versetzt, wodurch das- 4-Brommethylbenzolsulfonsäurebenzylamid zunächst ölig, aber nach kurzer Zeit in schönen Kristallen ausfällt. Es wird aus Alkohol in farblosen Blättchen vom Schmelzpunkt 132° erhalten.Example 2 27 g of 4-bromomethyl-benzenesulfonic acid chloride are dissolved in 75 cc of acetone, and a solution of 21 g of benzylamine in 50 cc of acetone is added. The mixture heats up. If the two reaction components are brought together too quickly, the acetone comes to the boil. After half-boiling on the water bath, the solution, which is filled with crystals of the benzylamine hydrochloride formed, is mixed with water, whereby the 4-bromomethylbenzenesulfonic acid benzylamide is initially oily, but after a short time precipitates in beautiful crystals. It is obtained from alcohol in colorless flakes with a melting point of 132 °.
Beispiel 3 Werden die Lösungen von 279 4-Brommethylbenzolsulfonsäurechlorid und 2o g a-Aminopyridin in Aqeton zusammengegeben, so tritt starke Erwärmung ein. Man hält 30 Minuten im Kochen und versetzt die Lösung hierauf mit Wasser, wodurch das 4-Brommethyl - benzolsulfonsäure-(a-aminopyridid) als bald kristallisierendes Öl ausfällt. Es wird aus Alkohol in farblosen Kristallen vom Schmelzpunkt t82° erbalten.EXAMPLE 3 If the solutions of 279 4-bromomethylbenzenesulphonic acid chloride and 20 g of a-aminopyridine in acetone are combined, the result is intense warming. The mixture is kept boiling for 30 minutes and water is then added to the solution, as a result of which 4-bromomethyl-benzenesulfonic acid (a-aminopyridide) precipitates as an oil which soon crystallizes. It is obtained from alcohol in colorless crystals with a melting point of t82 °.
Beispiel 4 35 g 4-Dibrommethyl-benzolsulfonsäurechlorid werden in ioo ccm Alkohol gelöst. In die Lösung trägt man 25 ccm 2oo/oiges wässeriges Ammoniak ein, wobei man die Temperatur nicht über 4o bis 50° steigen läßt. Beim Abkühlen erstarrt die Lösung zu einem Kristallbrei von 4-Dibrommethyl-benzolsulfonsäureamid. Es wird nach dem Absaugen gut ausgewaschen und aus Alkohol in Form farbloser Kristalle vom Schmelzpunkt 174' erhalten.Example 4 35 g of 4-dibromomethylbenzenesulfonic acid chloride are in ioo ccm of alcohol dissolved. 25 ccm of 2oo / o aqueous ammonia are carried into the solution a, whereby the temperature is not allowed to rise above 40 to 50 °. When cooling down the solution solidifies to form a crystal slurry of 4-dibromomethylbenzenesulfonic acid amide. It is washed out well after suction and from alcohol in the form of colorless crystals obtained from melting point 174 '.
In ähnlicher Weise können auch das 4-Dibrommethyl-benzolsulfonsäurediäthylamid (Schmelzpunkt 132°) und das 4-Dichlormethyl-benzolsulfonsäureamid (Schmelzpunkt 157°) gewonnen werden.4-Dibromomethylbenzenesulfonic acid diethylamide can also be used in a similar manner (Melting point 132 °) and 4-dichloromethylbenzenesulfonic acid amide (melting point 157 °).
Beispiel 5 279 trockenes 4-Bromm@ethyl-benzolsulfonsäurechlorid werden auf dem Wasserbad auf 8o° erwärmt. In die Schmelze trägt man unter Rühren 37g Dodecylamin ,ein, wobei die Temperatur auf 95' steigt. Nach dem Eintragen wird noch 5 Minuten gerührt und die Schmelze aus verdünntem Alkohol umkristallisiert. Beim Erkalten erhält man das 4-Brommethyl-benzolsulfonsäuredodecylamid in farblosen Blättchen vom Schmelzpunkt 96".Example 5 279 dry 4-bromom @ ethyl-benzenesulphonic acid chloride are heated to 80 ° on a water bath. 37 g of dodecylamine are introduced into the melt with stirring, the temperature rising to 95 °. After the addition, stirring is continued for 5 minutes and the melt is recrystallized from dilute alcohol. On cooling, the 4-bromomethylbenzenesulfonic acid dodecylamide is obtained in colorless flakes with a melting point of 96 ".
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2700D DE853444C (en) | 1940-08-09 | 1940-08-09 | Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2700D DE853444C (en) | 1940-08-09 | 1940-08-09 | Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE853444C true DE853444C (en) | 1952-10-23 |
Family
ID=7083411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF2700D Expired DE853444C (en) | 1940-08-09 | 1940-08-09 | Process for the preparation of p-alkyl-substituted benzenesulfonic acid amide compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE853444C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096897B (en) * | 1959-07-15 | 1961-01-12 | Hoechst Ag | Process for the preparation of substituted benzene-m-disulfon-amides |
| DE1104948B (en) * | 1960-01-05 | 1961-04-20 | Thomae Gmbh Dr K | Process for the production of 4-chlorobenzene-1, 3-di- (N-methyl-sulfonamide) |
| DE1111618B (en) * | 1959-10-23 | 1961-07-27 | Hoechst Ag | Process for the preparation of substituted benzene-m-disulfonamides |
-
1940
- 1940-08-09 DE DEF2700D patent/DE853444C/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096897B (en) * | 1959-07-15 | 1961-01-12 | Hoechst Ag | Process for the preparation of substituted benzene-m-disulfon-amides |
| DE1111618B (en) * | 1959-10-23 | 1961-07-27 | Hoechst Ag | Process for the preparation of substituted benzene-m-disulfonamides |
| DE1104948B (en) * | 1960-01-05 | 1961-04-20 | Thomae Gmbh Dr K | Process for the production of 4-chlorobenzene-1, 3-di- (N-methyl-sulfonamide) |
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